The present invention relates to novel agricultural and horticultural compositions having fungicidal properties. The compositions contain the known iminoctadine and acid addition salts thereof on the one hand and the known N-(2,3-dichloro-4-hydroxy-phenyl)-1-methyl-cyclohexane carboxamide on the other hand.
It has already been known that iminoctadine and acid addition salts thereof are effective against a broad range of diseases that occur in important crop plants (see JP-A Sho 62-209003). Further, it has been described already that N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexane carboxamide has a good fungicidal activity and is effective against gray mold in grapes and citrus fruits as well as against brown rot in peaches (see JP-A Hei 2-11551). However, the activity of these compounds is not always fully satisfactory for the control of severe infections with gray mold. Moreover, the control of gray mold fungus has become an even more serious problem due to the emergence of strains which are resistant to benzimidazoles, dicarboximides and diethofencarb
The present invention provides new compositions, which are excellently suitable for the control of phytopathogenic fungi, such as not only gray mold, but also fungal strains which are resistant to the above-mentioned agents. Furthermore, the compositions according to the invention are effective against a broad range of plant diseases even if the infection is severe.
The present invention has been completed after intensive research to resolve the above-mentioned problems. It has been found that compositions containing iminoctadine or acid addition salts thereof and N-(2,3-dichloro-4-hydroxy-phenyl)-1-methyl-cyclohexane carboxamide are very effective against fungi causing disease in plants, including not only gray mold, but also strains, which are resistant to the above-mentioned agents. It has also been found that the compositions according to the invention exert an excellent control effect even if the infection is severe.
It has been found now that the novel agricultural and horticultural fungicidal compositions containing as active ingredients a combination of
A) 1,1xe2x80x2-iminiodi(octamethylene)diguanidine of the formula 
xe2x80x83(iminoctadine) or an acid addition salt thereof and
B) N-(2,3-dichloro-4-hydroxy-phenyl)-1-methyl-cyclohexanecarboxamide of the formula 
xe2x80x83(fenhexamid)
exhibit a very good fungicidal activity.
Surprisingly, the fungicidal effect of the active compound combinations according to the invention is substantially greater than the sum of the effects of the individual active compounds. It is, therefore, a matter of an unforeseeable, genuine synergistic effect and not simply of an addition to the effect.
The 1,1xe2x80x2-iminiodi(octamethylene)diguanidine is characterized by the formula (I) and is known under the common name iminoctadine.
Acid addition salts of iminoctadine include carboxylates, sulfonates, hydrochloride, carbonate, lauryl sulfate, sulfate, phosphate and the like. Examples of carboxylates include acetate, oxalate, laurylate, oleate, citrate and the like. Examples of sulfonates include alkyl sulfonate, alkyl benzene sulfonate, and the like. Examples of alkyl sulfonates include lauryl sulfonate, dodecyl sulfonate and the like.
Examples of alkyl benzene sulfonates include dodecyl benzene sulfonate, p-toluene sulfonate and the like. Preferred acid addition salts are carboxylates and sulfonates, such as alkyl benzene sulfonates. Particularly preferred are alkyl benzene sulfonates having 1 to 18 carbon atoms, specifically 10 to 13 carbon atoms, in the alkyl group.
The 1,1xe2x80x2-iminiodi(octamethylene)diguanidinium tris(alkyl-benzenesulfonate) [iminoctadine-tris(albesilate)] may be mentioned as an example of an acid addition salt of iminoctadine. This compound can be represented by the following formula 
n=10 to 13.
[iminoctadine tris(albesilate)].
The iminoctadine of the formula (I) and acid addition salts thereof are known (see JP-A Sho 62-209003 and xe2x80x9cThe Pesticide Manualxe2x80x9d, 11th Edition 1997, pages 709-712).
The N-(2,3-dichloro-4-hydroxy-phenyl)-1-methyl-cyclohexane carboxamide of the formula (II) is also a known compound (see JP-A Hei 2-11551 and EP-A 0339418).
The synergistic effect is particularly clear when the active compounds are present in the compositions according to the invention in particular weight ratios. However, the weight ratios of the active compounds can be varied within a relatively wide range. In general, from 0.5 to 10 parts by weight, preferably from 1 to 5 parts by weight, of the compound of the formula (II) are allotted to 1 part by weight of a compound of group (A).
The agricultural and horticultural fungicidal compositions according to the invention possess very good fungicidal properties and can be used for the control of phytopathogenic fungi in agriculture and horticulture. They are suitable for the control of fungi, which are resistant to some other chemical compounds, and against fungi causing plant diseases, such as late blight, gray mold, leaf mold, leaf spot, anthracnose, and early blight in tomatoes; downy mildew, powdery mildew, gray mold anthracnose, gummy stem blight, phytophthora rot, scab, and Corynespora leaf spot in cucumbers; stem blight, leaf spot and gray mold in asparagus; anthracnose and gray mold in strawberries; powdery mildew, anthracnose, and gummy stem blight in pumpkins; Sclerotinia rot in cabbages; anthracnose in garland chrysanthemums; powdery mildew, Sclerotinia rot, anthracnose and gummy stem blight in watermelons; alternaria leaf spot, gray mold, and gray mold neck rot in onions; powdery mildew, gray mold and black rot in eggplants; alternaria leaf spot in welsh onions; leaf spot and alternaria leaf spot in Chinese cabbages; Sclerotinia rot and gray mold in peppers; powdery mildew, anthracnose, and gummy stem blight in melons; gray mold in lettuce; scab and gray mold in Japanese apricots; powdery mildew, anthracnose, gray mold and leaf spot in Japanese persimmons; gray mold and scab in citrus fruits; scab, black spot and physalospora canker in Japanese pears; gray mold, ripe rot, leaf spot, anthracnose, gummy stem blight, black rot, and swelling arm in grapes; scab, brown rot, Phomopsis rot, and anthracnose in peaches; scab, alternaria leaf spot/ring rot, blotch, sooty blotch, fly speck, fruit spot, and blossom blight in apples; stalk blight anthracnose, gray mold and Sclerotinia rot in Azuki beans; anthracnose, gray mold, and Sclerotinia rot in kidney beans; ring spot in broad beans; purple speck in soybeans; powdery mildew in tobacco; Romalaria leaf spot and cercospora leaf spot in sugar beets; anthracnose, gray blight, shoot blight and gray mold in tea; and black spot, anthracnose, gray mold, and powdery mildew in flowers. In particular, the agricultural and horticultural fungicidal compositions according to the invention are suitable for the control of fungi, which are resistant to some other chemical compounds, and against fungi causing plant diseases, such as gray mold in tomatoes, cucumbers, eggplants, and strawberries, or gray mold in fruits such as grapes, peaches, and citrus fruits.
The agricultural and horticultural fungicidal compositions can be used during the growing period of crops such as asparagus, strawberries, pumpkins, cabbages, cucumbers, garland chrysanthemums, watermelons, onions, tomatoes, eggplants, green onion, Chinese cabbages, peppers, spinach, Oriental melons, melons, lettuces, Japanese apricots, Japanese persimmons, citrus fruits, Japanese pears, grapes peaches, apples, Azuki beans, kidney beans, broad beans, soybeans, tobacco, sugar beets, tea, and flowers (i.e., roses, chrysanthemums, carnations, cyclamen, gentian, etc.). For grapes in particular, the agricultural and horticultural fungicidal composition can be preferably used between the stage prior to flowering and the young fruit stage in their growing period.
The agricultural and horticultural fungicidal compositions according to the invention can be used as such or in the form of customary formulations, such as wettable powders, suspension concentrates, dustable powders, emulsifiable concentrates, oil miscible liquids, tablets, granules, aerosols and the like. The formulations can be prepared by customary methods, for instance by mixing the active compounds with other components, such as extenders, surfactant agents, other additives, or suitable carriers, including water. The agricultural and horticultural fungicidal compositions according to the invention are preferably used in the form of wettable powders or suspension concentrates.
Examples of extenders include kaolins, clays, talc, chalk, quartz, attapulgite, montmorrillonite, diatomaceous earth, calcium carbonate, hydrated lime, quartz sand, ammonium sulfate, carbamide, vermiculite, wood chips, starch, clay, talc, bentonite, white carbon, etc., in the case of solid carriers, and alcohols, kerosene, naphtha, aromatic compounds (xylene, toluene, phenol, etc.), alkyl naphthalene, cyclohexane, benzene, acetone, N-methyl pyrrolidone and the like in the case of liquid carriers.
Examples of surfactant agents include polyoxysorbitan monooleate, ethylene oxide/propylene oxide copolymers, lignin sulfonate, sorbitan ester, soaps, alkyl benzene sulfonate, fatty acid amine salts, quaternary ammonium salts, alkyl pyridinium salts, alkyl aminoethyl glucine, alkyl dimethyl betaine, polyglycol sulfate ester, alkyl amino sulfonate, isopropyl phosphate, carboxymethyl cellulose, hydroxypropyl cellulose, xanthane gum, diaryl alkyl disulfonate, alcohol sulfate, alkyl aryl sulfonate, polyoxyethylene alkyl aryl ether, polyoxyethylene glycol ether, polyoxyethylene sorbitan monoalkylate, and the like.
Other additives include adjuvants like carboxymethyl cellulose, ethylene glycol and propylene glycol, as well as additives typically used during formulation.
The formulations generally contain between 30 and 90 per cent by weight of the active compounds, preferably between 50 and 80 per cent by weight. The active compounds can be present in the formulations in admixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, fertilizers and plant-growth regulators.
The agricultural and horticultural fungicidal composition according to the invention are preferably used in the form of dispersions, which can be obtained by diluting the formulations with water. It is also possible to add other fungicides or pesticides to the formulations and then to disperse them. The concentration of the active compounds in the dispersions can be varied according to the period of use, method, site, form of the agent, targeted disease and targeted crop. However, the range for the acid addition salt of the iminoctadine is between 25 and 24,000 ppm, preferably between 60 and 200 ppm (when using iminoctadine, between 7.8 and 7,500 ppm, preferably between 19 and 63 ppm), while the range for fenhexamid is between 100 and 40,000 ppm, preferably between 150 and 300 ppm. In particular, in the case where the composition is used for fruits such as grapes and peaches, the concentration of the active compounds in the dispersions is such that the range for the acetic acid salt of the iminoctadine is between 25 ppm and 24,000 ppm, preferably between 200 ppm and 1,000 ppm (when using iminoctadine, between 7.8 ppm and 7,500 ppm, preferably between 62 ppm and 313 ppm), while the range for the fenhexamid is between 100 ppm and 40,000 ppm, preferably between 250 ppm and 1,500 ppm.
The dispersing amount will vary depending on the period of use, method, site, form of the agent, target disease, target crop, etc. For example, when spraying over vegetables such as tomatoes and cucumbers, the amount of the agent in the concentration of the effective component that is dispersed is preferably between 150 and 300 L per 10 are, while when spraying over fruits such as grapes and peaches, the amount of agent in the concentration of the effective component that is dispersed is preferably between 200 and 700 L per 10 are.